Primary aromatic amine aldehyde resins, methods of hardening the same, and products thereof



Patented June 19,1945

PRIMARY AROMATIC AMINE ALDEHYDE RESINS, METHODS OF HARDENING THE SAME, AND PRODUCTS THEREOF Loring Coes, Jr., Brookfield, Masa, assignor to Norton Company, Worcester, Mass., a corporation of Massachusetts No Drawing. Application July 23, 1942, Serial No. 452,091 i 8 Claims.

This invention relates to resins and more particularly to the polymerized condensation product of a primary aromatic amine with formaldehyde.

One object of the invention is to provide a reagent which hardens a primary aromatic amine formaldehyde resin and particularly an aniline formaldehyde resin.

Another object is to provide an agent which not only hardens such resins but will also serve as a wettant for granular material bonded by the resin and as a plasticizer for the green mixture of grains and resin prior to the heat hardening stage.

Another object of the invention is to provid a hardening agent for such resins which during the heat conversion stage will not react to form water and cause distortion of the resin body.

Another object of the invention is to provide a method of making afinal resin product, or an intermediate product capable of producing the same, whereby a primary aromatic amine formald hyde resin may be materially hardened.

Another object is to provide a method of this type wherein a resin or a mixture of the resin with granular material to be bonded thereby may be cold-molded and the molded object thereafter heat cured while not confined under pressure.

Another object is to provide a method of making molded objects, with or without filling or granular material, with th aid of an agent serving as a wettant and a plasticizer for a primary aromatic amine formaldehyde resin prior to heat hardening and which ultimately acts as a hardening and cross-linking agent for the resin without producing water during the hardening stage or causing distortion of the formed body. Other objects will be in part obvious or in part pointed out hereinafter.

The invention accordingly consists in the compositions and products and in the several steps and relation and order of each of said steps to one or more of the others thereof, all as will be illustratively described herein, and the scope of the application of which will be indicated in the following claims. I

I provide a quantity of a primary aromatic amine, such as aniline, ortho, meta or para tpluidine, or diamino diphenylmethane; and a quantity of formaldehyde. I may optionally provide a quantity of one or more organic compounds containing a halogen selected from the group consisting of chlorine, bromine and iodine and capable of splitting of! hydrogen halide at elevated temperatures and/or of alkylating an aromatic amine polymer, providing cross links connecting amine groups of the chains. The aromatic amine which I now prefer to use is aniline. Aniline or one of the other aromatic amines mentioned, or mixtures of two or more of such amines, is reacted with formaldehyde HCHO in the presence of a strong acid to produce a long chain polymer which, when an excess of formaldehyde above the stoichiometric proportions i used, for example, 20% excess, has adjacent chains connected with methylene CH2 groups to form a tough, heat resistant, semi-thermoplastic resin. I may add some of the formaldehyde after the initial condensation, in the form of paraformaldehyde, or by the addition of hexa-methylenetetramine.

As examples of the halogenated organic compound, I may use any of polyvinyl chloride, polyvinylidene dichloride, rubber hydrochloride, chlorinated rubber, chlorinated polyisobutylene; any chlorine, bromine or iodine substituted paraffine hydrocarbon, such as hexa chlo-r ethane, tetra chlor pentane, 1,2, diiodo ethane, beta butylene bromide, partly chlorinated eicosane, or any aliphatic halohydrin of not mor than six carbon atoms, such as any of the amylene chlorhydrins; propylene chlorhydrin; any of the butylene chlorhydrins; ethylene chlorhydrin, ethylene bromhydrin, or glycerol alpha gamma dichlorhydrin. Naturally enough, most of the examples are chlorinated compounds; because these are cheaper and more readily available than the brominated or iodated compounds, but the latter two give efiectiv results. The fiuorinated compounds are rejected because they are too stable and will not alkylate the polymer. However, so far as the broad features of this invention are concerned, and apart from the esters hereinafter described, the halogenated organic compound may be omitted altogether.

Since one use of the resins of the invention relates to grinding wheels and other solid abrasive compositions and articles, I provide a quantity of abrasive grain. Any abrasive grain may be used, for example, any ofthe varieties of alumina, such as emery, corundum, dense regular fused alumina, porous white fused alumina; silicon carbide and other hard carbides quartz;

glass; garnet; or diamonds. Two or moreof these abraslves rhay be mixed, if desired.

Manufacturers usually prefer to use the dry granular mix method, with the cold press and the oven to make organic bonded grinding wheels because this combination of steps and features is thecheapest to carr out and, furthermore,

generally gives uniform results. In the dry granular mix method the abrasive grains are placed in a mixing pan and are then wet with a suitable liquid; then powdered fusible resin is added, mixing is done to coat each granule with some of the powder and to leave a minimum of loose powder, then a mold is charged with the dry granular mix thus produced, the top plate is inserted, the mold is closed by means of an hydraulic press, the mold is then "stripped, the green wheel is taken to an oven and (at the same time as hundreds or thousands of others of varying sizes, shapes and compositions) it is cured to make the final composition and, after truing" or shaving, the final article. This method, in contradisti'nction to the use of the hot press with or without the autoclave and vice versa, has the advantage that ordinary ovens, in which thousands of "green wheels can be stacked, are used; the hydraulic press is tied up by a given wheel for thirty seconds instead of thirty minutes, and the press need have no heated platens. This wetting of the abrasive grains by a liquid is called "plasticizing. It is preferred that the wettant be a solvent for the resin.

In the commercial manufacture of anilineformaldehyde resin bonded grinding wheels and other solid abrasive products, only furfural has been used as this plasticizer-wettant. (Other aromatic-amine-aldehyde polymers have not been used commercially for the manufacture of grinding wheels and other solid abrasive products so far as I am aware). The furfural cross links the polymer and, therefore, converts it to the infusible condition. A stoichlometric quantity of aniline and formaldehyde condensed in the presence of a strong acid is believed to produce a resin which is structurally represented thus:

Such a resin cross linked with furfural is believed to be represented thus:

mentioned halogenated organic compounds and with or without abrasive grains or other fillers and with or without suitable wettant plasticizers,

such as furiural. The reagents are capable of initially wetting and plasticizlng a green mixture of the resin and a suitable granular material and of ultimately reacting with the resin to harden the same. One preferred reagent is dl-monochloracetate of ethylene glycol. This ester is:

I believe it alkylates and cross-links with the aniline-formaldehyde polymer thus:

brittle.

Di-ethylene glycol di monochloracetate is written thus:

CH1C H20 c o -c H2Cl t oHPoHPooo-cHl-m Tri-ethylene glycol di-monochloracetate is .written thus:

Tri-methylene glycol di-monochloracetate is written thus:

These compounds are all esters and it will be seen that the four compounds are definitely related to each other and they might all be called glycol di-monochloracetates, and my invention consists in the use of any of them in the combination above explained in regard to ethylene glycol di-monochloracetate. However, thecompounds of large molecular weight, that is, having additional CaH4O groups are solids and are not usable in my invention. Therefore, I use any glycol di-monochloracetate selected from the group consisting of ethylene glycol di-monochloracetate, di-ethylene glycol di-monochloracetate, tri-ethylene glycol di-monochloracetate, and tri-methylene glycol di-monochloracetate.

The above-mentioned relationship between the four compounds appears also from the manner in which they cross-link with the aniline-formasvassa monochloracetate cross links with the above polymer thus:

n o1 &0

. CHr-C O C Hr-CH;

' O CHPHI CH: O

The tri-ethylene glycol di-monochloracetate cross-links with the polymer thus:

H Cl

The tri-methylene glycol di-monochloracetate cross-links with the above polymer thus:

In each case, it will be seen that chlorine appears in the amino group, and a grinding wheel, when made according to my invention, utilizing any of the glycol di-monochloracetates, or mixtures thereof, as wettant plasticizers and alkylating cross-linking agents, can release hydrogen chloride at the grinding line under the influence of the heat there generated. Illustrative examples of grinding wheels are set forth hereinafter.

My invention, however, consists also in the discovery of these compounds and in the discovery that they are capable of effective and efficient ooaction as hardening agents for aromatic amine aldehyde resins and that by appropriate admixture of the two, with or without fillers, a good, strong resin of appropriate hardness is produced. The mixture is readily moldable and may be hot pressed for curing and hardening or may be cold pressed and then baked, andin the latter instance it does not tie up, for substantial periods of time, expensive hot press equipment. The examples later herein set forth, give illustrations of both methods of hardening and though they are illustrations of the making of abrasive articles, these examples will suflice to illustrate the aspects of my inven-v tion now under consideration, for, for those purposes, the abrasive grains may be treated as fillers, but it will be understood that, in the making of abrasive articles, I am enabled to achieve certain unique coactions some of which, such as the liberation of hydrogen chloride at the grinding line, are above mentioned, and some others of which I mention later hereinafter.

Insofar as I am aware, the above-mentioned hardening agents are per so new compositions of matter and the manner of producing them will appear from the following illustration of a preferred way of making, according to my invention, di-ethylene glycol di-monochloracetate.

Thus, I may start with about 186 grams of chloracetic acid and 106 grams of di-ethylene glycol which I then heat in an open flask. at C. for 12 hours. The mixture is then poured into water and neutralized with sodium carbonate. The ester is then washed with water, dried over sodium sulphate and finally heated at 100 C. under a pressure of 20 millimeters for 3 hours to remove volatile impurities.

The di-monochloracetates of ethylene glycol, tri-ethylene glycol, and tri-methylene glycol may be made in the same manner, using the same stoichiometric proportions of reactants.

The esters prepared in this way are nearly colorless liquids, having a slight pleasant odor. When mixed with aniline formaldehyde resin, the latter in powdered form, the mix may be molded at room temperature, then removed from the mold, and cured in an oven; or the mix may be worked into a sheet of desired thickness, as on mixing rolls, the desired shape or conformation cut or stamped from the sheet and then cured in an oven, or the mix may be molded and hot pressed.

Several examples of the making up of abrasive articles will suflice to give concrete illustration of the various features of the various aspects of my invention; thus:-

Ezample I 525 grams of #46 grit Alundum abrasive grains are wet with 20 cc. of ethylene glycol dimonochloracetate, and here I find that this ester, as is true of the others, is a good wettant for the grain. To this is then added, with stirring, the dry powdered resin with or without other'ingredients, to make a dry granular mix and in this example I add grams of a mixture comprising, by volume, 65% of an aniline formaldehyde resin, 30% of cryolite, and 5% of soluble anhydrite. The resultant well stirred or well mixed dry granular mix is spread in a 6" mold (for making a grinding wheel) and is pressed to a pore volume of 15%, the molding and pressing being at room temperature.

The green wheel is then stripped from the mold and is cured in an oven; preferably I use an initial curing temperature of 95 C., gradually raising it over a period of 4 hours to 0., thereafter keeping the wheel at 175 C. for 2 hours and then cooling it slowly.

The di-monochloracetates of di-ethylene glycol, tri-ethylene glycol, and tri-methylene glycol may be used in the same manner, using substan tially the same proportions.

Example II ments, and, for making a grinding wheel, I add to the above-mentioned wetted grain 165 grams of a mixture comprising, by volume, 65% of an aniline formaldehyde resin, the latter in powdered form, 30% of cryolite, and 5% of soluble anhydrite. The resultant well mixed or stirred "dry granular mix is then worked on differential mixing rolls until it is formed into a sheet which is then passed through calender rolls to give it the desired thickness, in this example a thickness of A 12" disk is then cut from the sheet and the resultant "green wheel is then cured in an oven in the manner described in Example I above.

The other esters may be used in the same manner, using substantially the same proportions of ingredients as in this Example II.

The esters are good solvents for aniline formaldehyde resin, are good hardening agents therefor, and are good molding plasticizers. making abrasive articles such as grinding wheels, the esters are good wettants for the abrasive grains and in cross-linking with the polymer as above described, they coact to bring about in the final product, the release of hydrogen chloride at the grinding line, certain of the advantages of which have been pointed out above. In their cutting action, grinding wheels have a resemblanee to the cutting action of wheels bonded with hard rubber but I find that the esters make possible some variation in the grinding characteristics according to the work which the particular wheel is to do, and a substantial range of control may be effected.

Thus, for example, in the making of grinding wheels, I have found that the hardness of the wheel decreases in the order of mono-, di-, tri-, ethylene glycol di-monochloracetate and trimethylene glycol di-monochloracetate, that is, the wheels are softer in the order of the justnamed hardening agents employed, while intermediate grades of hardness can be achieved by using mixtures of two or more of the esters. Thus a wide range of grinding wheel characteristics can be achieved.

By way of further example, and generally stated, a wheel made up using tri-ethylene glycol di-monochloracetate may be said to have characteristics that permit it to be employed where a shellac-bonded wheel is suitable but comparative tests show a wheel wear (running wet) of 0.055 and a wheel wear (running dry) of 0.134 for the former as compared to 0.628 and 0.917

.(respectively wet and dry) for a shellac-bonded In a, generally similar way and generally stated, a wheel made up according to my invention and utilizing ethylene glycol di-monochloracetate as the wettant and hardening agent may be said to have characteristics that permit it to be used to do the work of a hard-rubber-bonded wheel, but comparative tests show a wheel wear (running wet) of 0.040 and a wheel wear (running dry) of 0.049 for the former as against 0.028 and 0.086 (re- When.

which test data are above set forth were all made up according to the proportions of ingredients illustrated in the foregoing Examples 1 and II, the wheel wear is set forth in square inches per out including also as to the shellac-bonded and rubber-bonded wheels, and the test data as to all of the wheels was obtained by cutting of! cold rolled steel with the wheels running at 9,500 surface feet per minute.

According to certain prior practices, difficulties are encountered during heat treatment or curing, due to the fact that swelling occurs; such swelling usually results from the formation of water and is aggravated by the conversion of water or possibly also of other constituents into vapors, under the action of the heat treatment. But according to my invention such disadvantages and defects are successfully overcome and I find that.

in practicing my invention, no such swelling occurs; this is due to the fact that no water or other liquid or vapors thereof, as would cause swelling, during the heat treatment or curing, are formed.

Ismake no claim herein to abrasive wheels or abrasive articles or to the method of making the same, that subject matter being claimed in my copending Patent No. 2,319,792 of May 25, 1943.

It will thus be seen that there has been provided by this invention, an article, a composition and a method in which the various objects hereinabove set forth together with many thoroughly practical advantages are successfully achieved. As various possible embodiments might be made of the mechanical features of the above invention and as the art herein described mightbe varied in various parts, all without departing from the scope of the invention. it is to be understood that all matter hereinabove set forth is to be interpreted as illustrative and not in a limiting sense.

I claim:

1. A resin comprising a primary aromatic amine formaldehyde resin alkylated by and cross linked with a resin-hardener comprising a compound selected from the group consisting of the mono-, di,- tri-, ethylene glycol di-monochloracetates and tri-methylene glycol di-monochloracetate.

2. An intermediate product that can be shaped or molded and heat treated for the formation of spectively wet and dry) in the case of a rubber- I bonded wheel.

Other tests of-wheels made according to my invention show a wheel wear of 0.063 (running wet) and a wheel wear of 0.173 (running dry) for a wheel in which di-ethylene glycol di-monoa resinous body comprising a mix of a primary aromatic amine formaldehyde resin and a hardening agent comprising a compound selected from the group consisting of the mono-, di-, tri-, ethylene glycol di-monochloracetates and trimethylene glycol di-monochloracetate.

3. In a method of making a resinous body, the steps which comprise making a mix comprising aniline formaldehyde resin and a hardening agent comprising a compound selected from the group consisting of the mono-, di-, tri-, ethylene glycol di-monochloracetates and tri-methylene glycol dimonochloracetate, and shaping and ouring the mix at curing temperature.

4. In a method of making a resinous body, the steps which comprise making a mix comprising a primary aromatic amine formaldehyde resin and a hardening agent comprising a compound selected from the group consisting of the mono-,

di-, tri-, ethylene glycol di-monochloracetates' and tri-methylene glycol di-monochloracetate, working the mix into sheet form of the desired thickness, cutting out of the sheet form the desired configuration of article, and then heattreating thelatter to harden the same.

5. In a method of making a resinous body, the

steps which comprise making a mix comprising a primary aromatic amine formaldehyde resin and a hardening agent comprising a compound selected from the group consisting of the mono-, di, tri-, ethylene glycol di-monochloracetates and tri-methylene glycol di-monochloracetate, cold molding the mix to the desired configuration, and then oven-treating it to harden the same.

6. The steps in a method of producing a moldable heat-settable intermediate product which 10 comprise adding to a primary aromatic amine formaldehyde resin a hardening agent comprising a compound selected from the group consisting of the mono-, di-, tri-, ethylene glycol di-monochloracetates and tri-methylene glycol di-mono- 15 tri-methylene glycol di-monochloracetate.

chloracetate, and mixing the same.

LORING GOES, JR. 

